Doping Silicon

The ease with which electrons in the semiconductor can be excited from the valence band to the conduction band depends on the band gap between the bands. The size of this energy bandgap serves as an arbitrary dividing line (roughly 4 eV) between semiconductors and insulators.

A pure semiconductor is often called an “intrinsic” semiconductor. The electronic properties and the conductivity of a semiconductor can be changed in a controlled manner by adding very small quantities of other elements, called “dopants”, to the intrinsic material. In crystalline silicon typically this is achieved by adding impurities of boron or phosphorus to the melt and then allowing the melt to solidify into the crystal. This process is called "doping".

Intrinsic Semiconductor: No impurities are added.

No. of electrons = No. of holes

You can change the behavior of silicon and turn it into a conductor by doping it. In doping, you mix a small amount of an impurity into the silicon crystal.

There are two types of impurities:

N-type - In N-type doping, phosphorus or arsenic is added to the silicon in small quantities. Phosphorus and arsenic each have five outer electrons, so they're out of place when they get into the silicon lattice. The fifth electron has nothing to bond to, so it's free to move around. It takes only a very small quantity of the impurity to create enough free electrons to allow an electric current to flow through the silicon. N-type silicon is a good conductor. Electrons have a negative charge, hence the name N-type.

P-type - In P-type doping, boron or gallium is the dopant. Boron and gallium each have only three outer electrons. When mixed into the silicon lattice, they form "holes" in the lattice where a silicon electron has nothing to bond to. The absence of an electron creates the effect of a positive charge, hence the name P-type. Holes can conduct current. A hole happily accepts an electron from a neighbor, moving the hole over a space. P-type silicon is a good conductor.

A minute amount of either N-type or P-type doping turns a silicon crystal from a good insulator into a viable (but not great) conductor -- hence the name "semiconductor."

N-type and P-type silicon are not that amazing by themselves; but when you put them together, you get some very interesting behavior at the junction. That's what happens in a diode.

Electrons excited to the conduction band also leave behind electron holes, i.e. unoccupied states in the valence band. Both the conduction band electrons and the valence band holes contribute to electrical conductivity. The holes themselves don't actually move, but a neighboring electron can move to fill the hole, leaving a hole at the place it has just come from, and in this way the holes appear to move, and the holes behave as if they were actual positively charged particles.

A donor atom that activates (that is, becomes incorporated into the crystal lattice) donates weakly bound valence electrons to the material, creating excess negative charge carriers. These weakly bound electrons can move about in the crystal lattice relatively freely and can facilitate conduction in the presence of an electric field. Its known as n-type impurity.

N type

Conversely, an activated acceptor produces a hole. It is known as a p-type impurity.

P Type

The n and p type designations indicate which charge carrier acts as the material's majority carrier. The opposite carrier is called the minority carrier, which exists due to thermal excitation at a much lower concentration compared to the majority carrier.

EFFECT OF DOPING:

A 1 cm³ specimen of a metal or semiconductor has of the order of 10²² atoms. In a metal every atom donates at least one free electron for conduction, thus 1 cm³ of metal contains on the order of 10²² free electrons. Whereas a 1 cm³ of sample pure germanium at 20 °C, contains about 4.2×10²² atoms and 2.5×10¹³ free electrons and 2.5×10¹³ holes (empty spaces in crystal lattice having positive charge). The addition of 0.001% of arsenic (an impurity) donates an extra 10¹⁷ free electrons in the same volume and the electrical conductivity is increased by a factor of 10,000.

• Carrier concentration

The concentration of dopant introduced to an intrinsic semiconductor determines its concentration and indirectly affects many of its electrical properties. The most important factor that doping directly affects is the material's carrier concentration.


In general, an increase in doping concentration affords an increase in conductivity due to the higher concentration of carriers available for conduction. Degenerately (very highly) doped semiconductors have conductivity levels comparable to metals and are often used in modern integrated circuits as a replacement for metal. Often superscript plus and minus symbols are used to denote relative doping concentration in semiconductors. For example, n⁺ denotes an n-type semiconductor with a high, often degenerate, doping concentration. Similarly, p^- would indicate a very lightly doped p-type material. It is useful to note that even degenerate levels of doping imply low concentrations of impurities with respect to the base semiconductor. In crystalline intrinsic silicon, there are approximately 5×10²² atoms/cm³. Doping concentration for silicon semiconductors may range anywhere from 10¹³ cm⁻³ to 10¹⁸ cm⁻³. Doping concentration above about 10¹⁸ cm⁻³ is considered degenerate at room temperature.

• Introducing new energy levels:

Doping a semiconductor crystal introduces allowed energy states within the band gap but very close to the energy band that corresponds to the dopant type. In other words, donor impurities create states near the conduction band while acceptors create states near the valence band. The gap between these energy states and the nearest energy band is usually referred to as dopant-site bonding energy or E_B and is relatively small. For example, the E_B for boron in silicon bulk is 0.045 eV, compared with silicon's band gap of about 1.12 eV. Because E_B is so small, it takes little energy to ionize the dopant atoms and create free carriers in the conduction or valence bands. Usually the thermal energy available at room temperature is sufficient to ionize most of the dopant.
Dopants also have the important effect of shifting the material's Fermi level towards the energy band that corresponds with the dopant with the greatest concentration. Since the Fermi level must remain constant in a system in thermodynamic equilibrium, stacking layers of materials with different properties leads to many useful electrical properties. For example, the p-n junction's properties are due to the energy band bending that happens as a result of lining up the Fermi levels in contacting regions of p-type and n-type material.

This effect is shown in a band diagram. The band diagram typically indicates the variation in the valence band and conduction band edges versus some spatial dimension, often denoted x.